WO2023059015A1 - Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative - Google Patents

Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative Download PDF

Info

Publication number
WO2023059015A1
WO2023059015A1 PCT/KR2022/014845 KR2022014845W WO2023059015A1 WO 2023059015 A1 WO2023059015 A1 WO 2023059015A1 KR 2022014845 W KR2022014845 W KR 2022014845W WO 2023059015 A1 WO2023059015 A1 WO 2023059015A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
negative electrode
active material
particle size
weight
Prior art date
Application number
PCT/KR2022/014845
Other languages
English (en)
Korean (ko)
Inventor
박수진
이재욱
이상민
Original Assignee
주식회사 엘지에너지솔루션
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020220007659A external-priority patent/KR20230048997A/ko
Application filed by 주식회사 엘지에너지솔루션 filed Critical 주식회사 엘지에너지솔루션
Priority to CN202280031910.9A priority Critical patent/CN117256057A/zh
Priority to JP2023566704A priority patent/JP2024515382A/ja
Priority to CA3220435A priority patent/CA3220435A1/fr
Priority to EP22878836.0A priority patent/EP4322248A1/fr
Publication of WO2023059015A1 publication Critical patent/WO2023059015A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to a negative electrode composition, a negative electrode for a lithium secondary battery including the negative electrode, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
  • a secondary battery is a representative example of an electrochemical device using such electrochemical energy, and its use area is gradually expanding.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharge rate have been commercialized and widely used.
  • an electrode for such a high-capacity lithium secondary battery research is being actively conducted on a method for manufacturing a high-density electrode having a higher energy density per unit volume.
  • a secondary battery is composed of an anode, a cathode, an electrolyte, and a separator.
  • the negative electrode includes a negative electrode active material for intercalating and deintercalating lithium ions from the positive electrode, and silicon-based particles having a high discharge capacity may be used as the negative electrode active material.
  • volume expansion itself is suppressed, such as a method of adjusting the driving potential, a method of additionally coating a thin film on the active material layer, and a method of adjusting the particle size of the silicon-based compound.
  • Various methods are being discussed to prevent the disconnection of the conductive path or the conductive path.
  • silicon-based negative electrodes still have disadvantageous characteristics of ion movement due to poor tortuosity structure due to the characteristics of silicon-based active material particles. Therefore, it is necessary to study the particle size distribution of the silicon-based active material itself, which can improve the conductive path.
  • Silicon-based negative electrodes still have disadvantageous characteristics of ion movement due to poor tortuosity structure due to the characteristics of silicon-based active material particles.
  • fine particles of silicon-based active material block the movement of ions, and also create a large number of SEI layers due to side reactions with fine particles during the charge/discharge cycle process, resulting in a rapid deterioration in diffusion resistance. found
  • the present application relates to a negative electrode composition capable of solving the above problems, a negative electrode for a lithium secondary battery including the same, a lithium secondary battery including the negative electrode, and a method for preparing the negative electrode composition.
  • An exemplary embodiment of the present specification is a silicon-based active material; cathode conductive material; and a negative electrode binder, wherein the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, and 1 part by weight or more of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material 5 parts by weight or less, and the silicon-based active material provides a negative electrode composition that satisfies the particle size ratio of Equations 1 and 2 below.
  • X1 represents the D5 particle size of the silicon-based active material
  • X2 represents the D95 particle size of the silicon-based active material
  • Y represents the central particle size (D50) of the silicon-based active material.
  • the negative electrode conductive material; and a negative electrode binder to form a mixture first mixing by adding water to the mixture; and adding a silicon-based active material to the mixed mixture and performing second mixing, wherein the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, Method for producing a negative electrode composition comprising 1 part by weight or more and 5 parts by weight or less of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material, and the silicon-based active material satisfies the particle size ratio of Equations 1 and 2 below provides
  • a negative electrode current collector layer In another exemplary embodiment, a negative electrode current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the negative electrode current collector layer.
  • the anode A negative electrode for a lithium secondary battery according to the present application; a separator provided between the anode and the cathode; And an electrolyte; it provides a lithium secondary battery comprising a.
  • the main object of the present invention is to solve the problem by controlling the fineness of silicon-based particles and using a silicon-based active material that satisfies a specific particle size range.
  • the silicon-based active material which is a high-capacity material
  • the silicon-based active material rather than adjusting the characteristics of the conductive material and the binder according to the volume expansion of the silicon-based active material, the silicon-based active material itself It is characterized by a change in characteristics.
  • the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, and contains 1 part by weight or more and 5 parts by weight or less of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material, and the silicon-based active material It is characterized in that the particle size distribution of is adjusted to the range of Equations 1 and 2 above.
  • the negative electrode composition according to the present application includes the silicon-based active material whose particle size distribution is controlled as described above, and as fine particles are removed from the viewpoint of tortuosity in the electrode, the movement (conductive path) of lithium ions becomes advantageous during charging and discharging.
  • the movement (conductive path) of lithium ions becomes advantageous during charging and discharging.
  • fine-grained silicon particles that interfere with the movement of lithium ions during charging and discharging react with lithium ions to cause a side reaction, which causes an increase in diffusion resistance, but includes silicon-based active materials controlled within the range of Formulas 1 and 2 according to the present application.
  • a lithium secondary battery using a silicon-based active material adjusted to a certain particle size range (range of Equation 1 and Equation 2) as in the present invention decreases lifespan and increases resistance during charging and discharging. can solve the problem of
  • FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application.
  • FIG. 2 is a diagram showing a laminated structure of an anode for a rechargeable lithium battery according to an exemplary embodiment of the present application.
  • FIG. 3 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
  • 'p to q' means a range of 'p or more and q or less'.
  • specific surface area is measured by the BET method, and is specifically calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mino II of BEL Japan. That is, in the present application, the BET specific surface area may mean the specific surface area measured by the above measuring method.
  • Dn means a particle size distribution, and means a particle size at the n% point of the cumulative distribution of the number of particles according to the particle size. That is, D50 is the particle size (central particle size) at the 50% point of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at the 90% point of the cumulative distribution of the number of particles according to the particle size, and D10 is the cumulative number of particles according to the particle size. It is the particle size at the 10% point of the distribution. Also, D95 is the particle size at the 95% point of the cumulative distribution of the number of particles according to the particle size, and D5 is the particle size at the 5% point of the cumulative distribution of the number of particles according to the particle size.
  • the central particle size can be measured using a laser diffraction method. Specifically, after dispersing the powder to be measured in a dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (e.g. Microtrac S3500) to measure the difference in diffraction pattern according to the particle size when the particles pass through the laser beam to distribute the particle size. yields
  • a laser diffraction particle size measuring device e.g. Microtrac S3500
  • the particle size or particle size may mean the average diameter or representative diameter of each grain constituting the metal powder.
  • a polymer includes a certain monomer as a monomer unit means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer.
  • this is interpreted as the same as that the polymer includes a monomer as a monomer unit.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using a commercially available monodisperse polystyrene polymer (standard sample) of various degrees of polymerization for molecular weight measurement as a standard material, and gel permeation chromatography (Gel Permeation It is the molecular weight in terms of polystyrene measured by chromatography; GPC).
  • molecular weight means a weight average molecular weight unless otherwise specified.
  • An exemplary embodiment of the present specification is a silicon-based active material; cathode conductive material; and a negative electrode binder, wherein the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, and 1 part by weight or more of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material 5 parts by weight or less, and the silicon-based active material provides a negative electrode composition that satisfies the particle size ratios of Formulas 1 and 2 above.
  • the silicon-based active material which is a high-capacity material
  • the silicon-based active material rather than adjusting the characteristics of the conductive material and the binder according to the volume expansion of the silicon-based active material, the silicon-based active material itself It is characterized by a change in characteristics.
  • the present invention includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, and includes 1 part by weight or more and 5 parts by weight or less of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material, It is characterized in that the particle size distribution of the active material is adjusted within the ranges of Equations 1 and 2 above.
  • a silicon-based active material in one embodiment of the present application, includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, and 1 part by weight or more of silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material 5 parts by weight or less, the ratio of D5 / D50 of the silicon-based active material is 20% or more, the ratio of D95 / D50 of the silicon-based active material may be 230% or less.
  • the ratio of Dx/Dy of the silicon-based active material may be calculated according to a general ratio calculation method, and may be expressed as (Dx/Dy) x 100 (%) as a calculation formula. That is, as an example, the ratio of D95/D50 of the silicon-based active material may be calculated as (D95/D50) X 100.
  • the silicon-based active material may be used as the silicon-based active material, particularly including pure silicon (Si) particles.
  • the silicon-based active material may include a metal impurity.
  • the impurity is a metal that may be generally included in the silicon-based active material, and may specifically include 0.1 parts by weight or less based on 100 parts by weight of the silicon-based active material. there is.
  • silicon-based active materials are used as negative electrode active materials to improve capacity performance, rather than adjusting the composition of the conductive material and the binder.
  • existing problems were solved by adjusting the particle size distribution of the active material itself.
  • the silicon-based active material may include silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less.
  • the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less means that it includes a plurality of individual silicon-based particles having a particle size within the above range, and the number of silicon-based particles included is not limited. .
  • the particle size of the silicon-based particles is spherical, it can be expressed as its diameter, but even if it is a shape other than spherical, the particle size can be measured in contrast to the case of the spherical shape, and is generally measured individually by a method in the art.
  • the particle size of silicon-based particles can be measured.
  • the silicon-based particles having a particle size of 1 ⁇ m or less may be included in an amount of 1 part by weight or more and 5 parts by weight or less.
  • the silicon-based particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material is 1 part by weight or more and 5 parts by weight or less, preferably 1 part by weight or more and 4 parts by weight or less, 1.2 parts by weight or more 4 parts by weight. May include the following.
  • the silicon-based active material according to the present invention has silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less and has silicon-based particles having a particle size of 1 ⁇ m or less in the above range, and the fine powder is controlled. It can be expressed as a silicon-based active material.
  • the silicon-based active material according to the present invention satisfies the above weight range, fine-grained silicon-based particles are removed to form an advantageous structure in terms of tortuosity in the electrode, thereby preventing an increase in diffusion resistance, and diffusition even if the charge/discharge cycle continues The rate at which the resistance increases can be greatly controlled. As a result of controlling the silicon-based active material having a small particle size in which side reactions with lithium ions occur, the lifespan and capacity of an electrode including the same are increased.
  • a negative electrode composition in which the ratio of D5/D50 of the silicon-based active material is 20% or more and the ratio of D95/D50 of the silicon-based active material is 230% or less.
  • the above formula may be applied, and specifically, (D5/D50) x 100 (%) and (D95/D50) x 100 (%) may be applied.
  • the ratio of D5/D50 of the silicon-based active material may be expressed by Equation 1 above.
  • Equation 1 may satisfy 20 ⁇ (X1 / Y) x 100 (%).
  • Equation 1 is 20 ⁇ (X1 / Y) x 100 (%), preferably 25 ⁇ (X1 / Y) x 100 (%), more preferably 30 ⁇ (X1 / Y) may be x 100 (%), (X1 / Y) x 100 (%) ⁇ 80, preferably (X1 / Y) x 100 (%) ⁇ 70, more preferably (X1 / Y) x
  • the range of 100 (%) ⁇ 55 may be satisfied.
  • the ratio of D5 / D50 of the silicon-based active material may be 20% or more, preferably 25% or more, more preferably 30% or more, 80% or less, preferably 70% or less , More preferably, the range of 55% or less may be satisfied.
  • the ratio of D95/D50 of the silicon-based active material may be expressed by Equation 2 above.
  • Equation 2 may satisfy (X2/Y) x 100(%) ⁇ 230.
  • the ratio of D95 / D50 of the silicon-based active material may satisfy a range of 230% or less, preferably 220% or less, most preferably 210% or less, and 180% or more, preferably may satisfy a range of 190% or more.
  • Equation 2 is (X2/Y) x 100(%) ⁇ 230, preferably (X2/Y) x 100(%) ⁇ 220, more preferably (X2/Y) x 100 (%) ⁇ 210 may be satisfied, and a range of 180 ⁇ (X2 / Y) x 100 (%), preferably 190 ⁇ (X2 / Y) x 100 (%) may be satisfied.
  • the D5 / D50 ratio (Equation 1) and the D95 / D50 ratio (Equation 2) of the silicon-based active material according to the present application are adjusted within the above ranges, an advantageous structure can be formed in terms of tortuosity in the electrode, and a charge-discharge cycle continuation Accordingly, the rate at which the diffusion resistance increases also has a feature that can be controlled.
  • Y represents the central particle size (D50) of the silicon-based active material.
  • D50 central particle size of the silicon-based active material.
  • Y may satisfy a range of 3 ⁇ m or more and 10 ⁇ m or less, preferably 4 ⁇ m or more and 7 ⁇ m or less, and more preferably 4.5 ⁇ m or more and 7 ⁇ m or less.
  • the X1 represents the D5 particle size of the silicon-based active material. Specifically, the X1 may satisfy a range of 2 ⁇ m or more and 5 ⁇ m or less, preferably 2.3 ⁇ m or more and 4 ⁇ m or less, more preferably 2.5 ⁇ m or more and 4 ⁇ m or less.
  • X2 represents a D95 particle size of the silicon-based active material.
  • the X2 may satisfy a range of 6 ⁇ m or more and 15 ⁇ m or less, preferably 7 ⁇ m or more and 14 ⁇ m or less, more preferably 8 ⁇ m or more and 14 ⁇ m or less.
  • a negative electrode composition in which the ratio of D5/D95 of the silicon-based active material is 20% or more is provided.
  • the silicon-based active material provides a negative electrode composition that satisfies the particle size ratio of Equation 3 below.
  • X1 represents the D5 particle size of the silicon-based active material
  • X2 represents the D95 particle size of the silicon-based active material.
  • Equation 3 is 10 ⁇ (X1 / X2) x 100 (%), preferably 15 ⁇ (X1 / X2) x 100 (%), more preferably 20 ⁇ (X1 / X2) may satisfy the range of x 100 (%), (X1 / X2) x 100 (%) ⁇ 70, preferably (X1 / X2) x 100 (%) ⁇ 60, more preferably (X1 / X2) x 100 (%) ⁇ 55 may be satisfied.
  • the silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less provides a negative electrode composition in which the full width at half maximum is 1 ⁇ m or more and 5 ⁇ m or less.
  • Particle size distribution in this application means a list of values or a mathematical function that defines the relative amount of particles present according to size. This can provide information about the particle size span width, and D10, D50 and D90 (known as the D-value or 3-point specification) are the most widely used values in PSD analysis. These values represent particle diameters at 10%, 50% and 90% of the cumulative distribution, respectively.
  • D50 is assumed to be 100 nm, it means that 50% of the particles in the sample are larger than 100 nm and 50% are smaller than 100 nm. Additional parameters related to the size distribution can be calculated as D10, D50, and D90, specifically Span can be calculated as follows.
  • Dmax of the silicon-based active material may satisfy a range of 30 ⁇ m or less. Specifically, Dmax may satisfy a range of 30 ⁇ m or less, 27 ⁇ m or less, and may satisfy 10 ⁇ m or more.
  • Dmin of the silicon-based active material may satisfy a range of 0.5 ⁇ m or more. Specifically, Dmin may satisfy a range of 0.5 ⁇ m or more and 1 ⁇ m or more, and may satisfy a range of 5 ⁇ m or less.
  • the Dmax and Dmin may mean the particle size of the silicon-based particle having the largest particle size (Dmax) and the smallest particle size (Dmin) in the silicon-based active material including the silicon-based particle.
  • the silicon-based active material generally has a characteristic BET surface area.
  • the BET surface area of the silicon-based active material is preferably 0.01 m 2 /g to 150.0 m 2 /g, more preferably 0.1 m 2 /g to 100.0 m 2 /g, particularly preferably 0.2 m 2 /g to 80.0 m 2 /g, most preferably from 0.2 m 2 /g to 18.0 m 2 /g.
  • the BET surface area is measured according to DIN 66131 (using nitrogen).
  • the silicon-based active material may exist, for example, in a crystalline or amorphous form, and is preferably not porous.
  • the silicon particles are preferably spherical or fragment-shaped particles. Alternatively but less preferably, the silicon particles may also have a fibrous structure or be present in the form of a silicon-comprising film or coating.
  • the silicon-based active material provides a negative electrode composition that is 60 parts by weight or more based on 100 parts by weight of the negative electrode composition.
  • the silicon-based active material may be 60 parts by weight or more, preferably 65 parts by weight or more, more preferably 70 parts by weight or more based on 100 parts by weight of the negative electrode composition, and 95 parts by weight or less, preferably may be 90 parts by weight or less, more preferably 80 parts by weight or less.
  • the negative electrode composition according to the present application has a feature that can solve the problem of resistance increase and lifespan reduction through adjustment according to the particle size of the silicon-based active material itself. .
  • the silicon-based active material may have a non-spherical shape and its sphericity is, for example, 0.9 or less, for example, 0.7 to 0.9, for example 0.8 to 0.9, for example 0.85 to 0.9 am.
  • the circularity (circularity) is determined by the following formula A-1, A is an area, P is a boundary line.
  • the negative electrode conductive material may include at least one selected from the group consisting of a point-shaped conductive material, a planar conductive material, and a linear conductive material.
  • the dotted conductive material may be used to improve the conductivity of the negative electrode, and has conductivity without causing chemical change, and means a spherical or dotted conductive material.
  • the point-shaped conductive material is natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, conductive fiber, fluorocarbon, aluminum powder, nickel powder, zinc oxide, It may be at least one selected from the group consisting of potassium titanate, titanium oxide, and polyphenylene derivatives, and may preferably include carbon black in terms of high conductivity and excellent dispersibility.
  • the point-shaped conductive material may have a BET specific surface area of 40 m 2 /g or more and 70 m 2 /g or less, preferably 45 m 2 /g or more and 65 m 2 /g or less, more preferably 50 m 2 / g or less . /g or more and 60 m 2 /g or less.
  • the point-like conductive material may satisfy a functional group content (Volatile matter) of 0.01% or more and 1% or less, preferably 0.01% or more and 0.3% or less, more preferably 0.01% or more and 0.1% or less. there is.
  • a functional group content Volatile matter
  • the present application is characterized in that it includes a silicon-based active material and a dotted conductive material having a functional group content within the above range, the control of the functional group content can be adjusted according to the degree of heat treatment of the dotted conductive material there is.
  • a high functional group content means a lot of foreign substances, and a low functional group content may mean more heat treatment.
  • the particle diameter of the dotted conductive material may be 10 nm to 100 nm, preferably 20 nm to 90 nm, and more preferably 20 nm to 60 nm.
  • the conductive material may include a planar conductive material.
  • the planar conductive material is a plate-shaped conductive material or a bulk type conductive material that can improve conductivity by increasing surface contact between silicon particles in the negative electrode and at the same time suppress the disconnection of the conductive path due to volume expansion.
  • the planar conductive material may include at least one selected from the group consisting of plate-like graphite, graphene, graphene oxide, and graphite flakes, and preferably may be plate-like graphite.
  • the average particle diameter (D50) of the planar conductive material may be 2 ⁇ m to 7 ⁇ m, specifically 3 ⁇ m to 6 ⁇ m, and more specifically 4 ⁇ m to 5 ⁇ m. .
  • D50 average particle diameter
  • the planar conductive material provides a negative electrode composition in which D10 is 0.5 ⁇ m or more and 1.5 ⁇ m or less, D50 is 2.5 ⁇ m or more and 3.5 ⁇ m or less, and D90 is 7.0 ⁇ m or more and 15.0 ⁇ m or less.
  • the planar conductive material is a high specific surface area planar conductive material having a high BET specific surface area; Alternatively, a planar conductive material having a low specific surface area may be used.
  • the planar conductive material includes a high specific surface area planar conductive material;
  • a planar conductive material with a low specific surface area can be used without limitation, but in particular, the planar conductive material according to the present application can be affected to some extent in the electrode performance by the dispersion effect, so that a planar conductive material with a low specific surface area that does not cause a problem in dispersion is used. may be particularly desirable.
  • the planar conductive material may have a BET specific surface area of 5 m 2 /g or more.
  • the planar conductive material may have a BET specific surface area of 5 m 2 /g or more and 500 m 2 /g or less, preferably 5 m 2 /g or more and 300 m 2 /g or less, more preferably 5 m 2 /g or more. g or more and 250 m 2 /g or less.
  • the planar conductive material is a high specific surface area planar conductive material, and the BET specific surface area is 50 m 2 /g or more and 500 m 2 /g or less, preferably 80 m 2 /g or more and 300 m 2 /g or less, more preferably Preferably, a range of 100 m 2 /g or more and 300 m 2 /g or less may be satisfied.
  • the planar conductive material is a planar conductive material with a low specific surface area, and the BET specific surface area is 5 m 2 /g or more and 40 m 2 /g or less, preferably 5 m 2 /g or more and 30 m 2 /g or less, more preferably Preferably, a range of 5 m 2 /g or more and 25 m 2 /g or less may be satisfied.
  • Other conductive materials may include linear conductive materials such as carbon nanotubes.
  • the carbon nanotubes may be bundled carbon nanotubes.
  • the bundled carbon nanotubes may include a plurality of carbon nanotube units.
  • the term 'bundle type' herein means, unless otherwise specified, a bundle in which a plurality of carbon nanotube units are arranged side by side or entangled in substantially the same orientation with axes in the longitudinal direction of the carbon nanotube units. It refers to a secondary shape in the form of a bundle or rope.
  • the carbon nanotube unit has a graphite sheet having a cylindrical shape with a nano-sized diameter and an sp2 bonding structure.
  • the characteristics of a conductor or a semiconductor may be exhibited according to the angle and structure of the graphite surface being rolled.
  • the bundled carbon nanotubes can be uniformly dispersed during manufacturing of the negative electrode, and the conductivity of the negative electrode can be improved by smoothly forming a conductive network in the negative electrode.
  • the linear conductive material is SWCNT; or MWCNTs.
  • the negative electrode conductive material is provided in an amount of 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the negative electrode composition.
  • the negative electrode conductive material is 10 parts by weight or more and 40 parts by weight or less, preferably 10 parts by weight or more and 30 parts by weight or less, more preferably 15 parts by weight or more and 25 parts by weight based on 100 parts by weight of the negative electrode composition. May include the following.
  • the negative electrode conductive material is a planar conductive material; And it provides a negative electrode composition comprising a linear conductive material.
  • the negative electrode conductive material is a planar conductive material; and a linear conductive material, wherein the linear conductive material is 0.01 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the negative electrode conductive material; and 90 parts by weight or more and 99.99 parts by weight or less of the planar conductive material.
  • the linear conductive material is 0.01 parts by weight or more and 10 parts by weight or less, preferably 0.05 parts by weight or more and 5 parts by weight or less, more preferably 0.1 parts by weight or more based on 100 parts by weight of the negative electrode conductive material 3 It may be less than parts by weight.
  • the planar conductive material is 90 parts by weight or more and 99.99 parts by weight or less based on 100 parts by weight of the negative electrode conductive material, preferably 95 parts by weight or more and 99.95 parts by weight or less, more preferably 97 parts by weight or more and 99.9 parts by weight or more. parts by weight or less.
  • the negative electrode conductive material includes a planar conductive material and a linear conductive material and satisfies the composition and ratio, respectively, it does not significantly affect the lifespan characteristics of an existing lithium secondary battery, and charging And the number of points where discharge is possible increases, resulting in excellent output characteristics at a high C-rate.
  • the negative electrode conductive material according to the present application has a completely different configuration from the positive electrode conductive material applied to the positive electrode. That is, in the case of the anode conductive material according to the present application, it serves to hold the contact between silicon-based active materials whose volume expansion of the electrode is very large due to charging and discharging. As a role of imparting, its composition and role are completely different from those of the negative electrode conductive material of the present invention.
  • the negative electrode conductive material according to the present application is applied to a silicon-based active material, and has a completely different configuration from that of a conductive material applied to a graphite-based active material. That is, since the conductive material used in the electrode having the graphite-based active material simply has smaller particles than the active material, it has characteristics of improving output characteristics and imparting some conductivity, unlike the negative electrode conductive material applied together with the silicon-based active material as in the present invention. The composition and role are completely different.
  • the planar conductive material used as the above-described negative electrode conductive material generally has a different structure and role from a carbon-based active material used as a conventional negative electrode active material.
  • the carbon-based active material used as the negative electrode active material may be artificial graphite or natural graphite, and refers to a material processed into a spherical or dotted shape to facilitate storage and release of lithium ions.
  • the planar conductive material used as the negative electrode conductive material is a material having a planar or plate-shaped shape, and may be expressed as plate-shaped graphite. That is, as a material included to maintain a conductive path in the negative active material layer, it means a material used to secure a conductive path in a planar shape inside the negative active material layer, rather than playing a role in storing and releasing lithium.
  • plate-like graphite is used as a conductive material means that it is processed into a planar or plate-like shape and used as a material that secures a conductive path rather than a role of storing or releasing lithium.
  • the negative active material included together has high capacity characteristics for storing and releasing lithium, and serves to store and release all lithium ions transferred from the positive electrode.
  • a carbon-based active material as an active material means that it is processed into a point shape or sphere and used as a material that stores or releases lithium.
  • artificial graphite or natural graphite which is a carbon-based active material
  • the plate-like graphite which is a planar conductive material, may have a planar BET specific surface area of 5 m 2 /g or more.
  • the negative electrode binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene -Selected from the group consisting of propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen is substituted with Li, Na or Ca, etc. It may include at least one that is, and may also include various copolymers thereof.
  • PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • the negative electrode binder serves to hold the active material and the conductive material in order to prevent distortion and structural deformation of the negative electrode structure in volume expansion and relaxation of the silicon-based active material.
  • All of the binders can be applied, specifically, a water-based binder can be used, and more specifically, a PAM-based binder can be used.
  • the negative electrode binder may be 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less, 5 parts by weight or more, 10 parts by weight based on 100 parts by weight of the negative electrode composition. may be more than
  • X1 represents the D5 particle size of the silicon-based active material
  • X2 represents the D95 particle size of the silicon-based active material
  • Y represents the central particle size (D50) of the silicon-based active material.
  • a negative electrode conductive material; and a negative electrode binder to form a mixture first mixing by adding water to the mixture; and adding a silicon-based active material to the mixed mixture and performing second mixing, wherein the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 ⁇ m or more and 30 ⁇ m or less, 1 part by weight or more and 5 parts by weight or less of Si particles having a particle size of 1 ⁇ m or less based on 100 parts by weight of the silicon-based active material, the ratio of D5 / D50 of the silicon-based active material is 20% or more, and the D95 / D50 of the silicon-based active material A method for producing a negative electrode composition having a ratio of 230% or less is provided.
  • each composition included in the negative electrode composition may be the same as described above.
  • the first mixing and the second mixing step is mixing at 2,000 rpm to 3,000 rpm for 10 minutes to 60 minutes.
  • the negative current collector layer In one embodiment of the present application, the negative current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present application formed on one side or both sides of the negative electrode current collector layer.
  • FIG. 1 is a diagram showing a laminated structure of a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application. Specifically, the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and FIG. 1 shows that the negative electrode active material layer is formed on one surface, but the negative electrode collector It can be included on both sides of the entire layer.
  • FIG. 2 is a diagram showing a laminated structure of a negative electrode for a rechargeable lithium battery according to an exemplary embodiment of the present application.
  • the negative electrode active material layer is included on both sides of the negative electrode current collector layer, and the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on both sides of the negative electrode current collector layer 10 can be confirmed. It is rare to substantially coat the single surface as shown in FIG. 1, and as shown in FIG. 2, the active material layer may be coated on both sides of the current collector layer.
  • the negative electrode composition of the present invention is included on at least one surface of the current collector layer, it is possible to manufacture a negative electrode.
  • composition of the active material layer coated on both sides may be the same or different from each other, and when the composition is different, a commonly used active material layer such as carbon-based or silicon-based may be used, and most preferably, both sides according to the present application A negative electrode active material layer containing the negative electrode composition is coated.
  • the negative electrode for a lithium secondary battery may be formed by applying and drying a negative electrode slurry including the negative electrode composition on one or both surfaces of a negative electrode current collector layer.
  • the negative electrode slurry is the negative electrode composition described above;
  • a slurry solvent may include.
  • the solid content of the negative electrode slurry may satisfy 5wt% or more and 40wt% or less.
  • the solid content of the negative electrode slurry may satisfy a range of 5wt% or more and 40wt% or less, preferably 7wt% or more and 35wt% or less, and more preferably 10wt% or more and 30wt% or less.
  • the solid content of the negative electrode slurry may refer to the content of the negative electrode composition included in the negative electrode slurry, and may refer to the content of the negative electrode composition based on 100 parts by weight of the negative electrode slurry.
  • the negative electrode active material layer can be efficiently formed by minimizing particle aggregation of the negative electrode composition due to appropriate viscosity when forming the negative electrode active material layer.
  • the slurry solvent may be used without limitation as long as it can dissolve the negative electrode composition, and specifically, water or NMP may be used.
  • the negative current collector layer generally has a thickness of 1 ⁇ m to 100 ⁇ m.
  • Such an anode current collector layer is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
  • a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
  • fine irregularities may be formed on the surface to enhance the bonding strength of the negative active material, and may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.
  • the negative electrode current collector layer has a thickness of 1 ⁇ m or more and 100 ⁇ m or less, and the negative electrode active material layer has a thickness of 20 ⁇ m or more and 500 ⁇ m or less.
  • the thickness may be variously modified depending on the type and purpose of the negative electrode used, but is not limited thereto.
  • the porosity of the negative electrode active material layer may satisfy a range of 10% or more and 60% or less.
  • the porosity of the negative electrode active material layer may satisfy a range of 10% or more and 60% or less, preferably 20% or more and 50% or less, and more preferably 30% or more and 45% or less.
  • the porosity is a silicon-based active material included in the negative electrode active material layer; conductive material; And as changed according to the composition and content of the binder, in particular, the silicon-based active material according to the present application; And it is characterized in that it satisfies the above range by including a specific composition and content of the conductive material, so that the electrode has an appropriate range of electrical conductivity and resistance.
  • FIG. 3 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
  • the negative electrode 100 for a lithium secondary battery including the negative electrode active material layer 20 on one surface of the negative electrode current collector layer 10 can be confirmed, and the positive electrode active material layer 40 on one surface of the positive electrode current collector layer 50
  • the positive electrode 200 for a lithium secondary battery including a and the negative electrode 100 for a lithium secondary battery and the positive electrode 200 for a lithium secondary battery are formed in a laminated structure with a separator 30 interposed therebetween.
  • a secondary battery may include the anode for a lithium secondary battery described above.
  • the secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • stainless steel, aluminum, nickel, titanium, fired carbon, or carbon on the surface of aluminum or stainless steel. , those surface-treated with nickel, titanium, silver, etc. may be used.
  • the cathode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and adhesion of the cathode active material may be increased by forming fine irregularities on the surface of the current collector.
  • it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
  • the cathode active material may be a commonly used cathode active material.
  • the cathode active material may include layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ), or compounds substituted with one or more transition metals; lithium iron oxides such as LiFe 3 O 4 ; lithium manganese oxides such as Li 1+c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , V 2 O 5 , and Cu 2 V 2 O 7 ; Represented by the formula LiNi 1-c2 M c2 O 2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01 ⁇ c2 ⁇ 0.3) Ni site-type lithium nickel oxide; Formula
  • the positive electrode active material layer may include a positive electrode conductive material and a positive electrode binder together with the positive electrode active material described above.
  • the positive electrode conductive material is used to impart conductivity to the electrode, and in the configured battery, any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
  • any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
  • Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers such as copper, nickel, aluminum, and silver; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one of them alone or a mixture of two or more may be used.
  • the positive electrode binder serves to improve adhesion between particles of the positive electrode active material and adhesion between the positive electrode active material and the positive electrode current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and the like may be used alone or in a mixture of two or more of them.
  • PVDF polyvinylidene fluoride
  • PVDF-co-HFP vinylidene fluoride-
  • the separator separates the negative electrode and the positive electrode and provides a passage for the movement of lithium ions. If it is normally used as a separator in a secondary battery, it can be used without particular limitation. Excellent is desirable.
  • a porous polymer film for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
  • porous non-woven fabrics for example, non-woven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers, and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used in a single-layer or multi-layer structure.
  • electrolyte examples include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in manufacturing a lithium secondary battery.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyllolactone, 1,2-dimethine Toxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxorane, formamide, dimethylformamide, dioxorane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, propionic acid
  • An aprotic organic solvent such as ethyl may be used.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates
  • an electrolyte having high electrical conductivity can be made and can be used more preferably.
  • the metal salt may be a lithium salt, and the lithium salt is a material that is soluble in the non-aqueous electrolyte.
  • the anion of the lithium salt is F - , Cl - , I - , NO 3 - , N (CN ) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C
  • the electrolyte may include, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
  • haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included.
  • One embodiment of the present invention provides a battery module including the secondary battery as a unit cell and a battery pack including the same. Since the battery module and the battery pack include the secondary battery having high capacity, high rate and cycle characteristics, a medium or large-sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system can be used as a power source for
  • a silicon-based active material satisfying the particle size and weight ratio of Table 1 below, a first conductive material, a second conductive material, and polyacrylamide as a binder were added to distilled water as a solvent for forming a negative electrode slurry at a weight ratio of 80:9.6:0.4:10
  • a negative electrode slurry was prepared (solid content concentration: 25% by weight).
  • the first conductive material was plate-shaped graphite (specific surface area: 17 m 2 /g, average particle diameter (D50): 3.5 ⁇ m), and the second conductive material was SWCNT.
  • the silicon-based active material is added and then 2500 rpm, 30 min. Dispersing to prepare a negative electrode slurry did
  • both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130 ° C. for 10 hours
  • a negative electrode active material layer was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
  • Formula 1 can be calculated as (D5/D50) x 100 (%)
  • Formula 2 is (D95/D50) x 100 (%)
  • Formula 3 is (D5/D95) x 100 (%) ) can be calculated as
  • the ratio of silicon-based particles having a particle size of 1 ⁇ m or less may indicate a weight ratio based on 100 parts by weight of the silicon-based active material.
  • Example 1 the silicon-based active material, the first conductive material, the second conductive material, the third conductive material, and polyacrylamide as a binder were used as a solvent for forming a negative electrode slurry in a weight ratio of 80:5:4.6:0.4:10
  • An anode was prepared in the same manner as in Example 1, except that distilled water was added to prepare a cathode slurry.
  • the first conductive material of Example 4 is carbon black (specific surface area: 58 m 2 /g, diameter: 37 nm), and the second conductive material of Example 4 is plate-shaped graphite (specific surface area: 17 m 2 /g, Average particle diameter (D50): 3.5 ⁇ m), and the third conductive material of Example 4 was SWCNT.
  • Example 1 except that the negative electrode slurry was prepared by adding polyacrylamide as a silicon-based active material, the first conductive material and a binder to distilled water as a solvent for forming the negative electrode slurry at a weight ratio of 80:10:10.
  • a negative electrode was prepared in the same manner as in 1.
  • the first conductive material of Example 5 was carbon black (specific surface area: 58 m 2 /g, diameter: 37 nm).
  • LiNi 0.6 Co 0.2 Mn 0.2 O 2 (average particle diameter (D50): 15 ⁇ m) as a cathode active material, carbon black (product name: Super C65, manufacturer: Timcal) as a conductive material, and polyvinylidene fluoride (PVdF) as a binder.
  • a positive electrode slurry was prepared by adding N-methyl-2-pyrrolidone (NMP) as a solvent for forming a positive electrode slurry at a weight ratio of 1.5:1.5 (solid content concentration: 78% by weight).
  • NMP N-methyl-2-pyrrolidone
  • both sides of an aluminum current collector were coated with the positive electrode slurry at a loading amount of 537 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a positive electrode
  • An active material layer was formed to prepare a positive electrode (anode thickness: 77 ⁇ m, porosity: 26%).
  • Secondary batteries were manufactured by injecting an electrolyte through a polyethylene separator between the positive electrode and the negative electrode of Examples 1 to 5 and Comparative Examples 1 to 3, respectively.
  • the electrolyte is an organic solvent in which fluoroethylene carbonate (FEC) and diethyl carbonate (DMC) are mixed in a volume ratio of 30:70, vinylene carbonate is added in an amount of 3% by weight based on the total weight of the electrolyte, and LiPF as a lithium salt 6 was added at a concentration of 1M.
  • FEC fluoroethylene carbonate
  • DMC diethyl carbonate
  • the secondary battery is 1) charged (0.33C CC/CV charge 4.2V 0.05C cut) and discharged (0.33C CC discharge 3.0V cut), this is the first cycle, and 2) charge (1.0C CC/CV charge 4.2V) 0.05C cut) and discharge (0.5C CC discharge, 3.0V cut) conditions, the cycle from the second cycle until the capacity retention rate reached 80% was checked to conduct charging and discharging.
  • the N-th capacity retention rate was evaluated by the following formula. The results are shown in Table 2 below.
  • Capacity retention rate (%) ⁇ (discharge capacity at the Nth cycle)/(discharge capacity at the first cycle) ⁇ ⁇ 100
  • Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Lifetime assessment (times@SoH80%) 275 274 273 270 265 250 255 241 Discharge resistance increase rate (%) 97 101 115 140 153 220 214 226
  • the silicon-based active materials according to Examples 1 to 5 satisfy the characteristics according to the present application, it was confirmed that the particulate silicon-based particles were removed to form a structure advantageous in terms of tortuosity in the electrode, thereby preventing an increase in diffusion resistance. .
  • the speed at which the diffusion resistance increases according to the removal of the fine silicon particles can be greatly controlled, and the lifespan and capacity of the electrode including the same can be greatly increased according to Examples 1 to 5.
  • Comparative Example 1 corresponds to a case in which the range of Equation 1 is not satisfied
  • Comparative Example 2 corresponds to a case in which Equation 2 is not satisfied
  • Comparative Example 3 corresponds to a case in which both Equations 1 and 2 are not satisfied. in case it does not In this case, compared to Examples 1 to 5, it was confirmed that the lifespan and the rate of increase in discharge resistance were not good due to side reactions occurring during the charge/discharge process by including a pure silicon active material in which the fine powder was not controlled.
  • Comparative Examples 1 to 3 it was confirmed that they contained finely divided silicon particles and had an unfavorable structure from the viewpoint of electrode tortuosity, and also, according to the repeated charging and discharging, the reaction between the finely divided silicon particles and lithium ions resulted in the SEI layer It was confirmed that the rate of increase in diffusion resistance increased due to formation, and the lifespan and resistance increase rate were not good.
  • Examples 1 to 3 correspond to the case of using a planar conductive material and a linear conductive material as conductive materials (two types of conductive materials).
  • Example 4 type 3 conductive material
  • Example 5 type 1 conductive material
  • the life evaluation result is particularly excellent and the discharge resistance increase rate is also low.
  • the two types of conductive materials do not significantly affect the lifespan characteristics of existing lithium secondary batteries, the number of points available for charging and discharging increases as the number of conductive paths increases, and the output characteristics are excellent at high C-rates. Because.
  • the negative electrode prepared in Example 1 and Comparative Example 1 was punched out with a 15 pie puncher to assemble a coin cell using two electrodes having similar thickness and weight (negative electrode/separator/negative electrode, same as electrolyte). After sufficiently impregnating the electrolyte, the pore resistance of the electrode was measured by measuring EIS at 100 points from 300 kHz to 100 mHz with an amplitude of 5 mV at room temperature, and the results are shown in Table 3 below.
  • the negative electrode including the silicon-based active material according to the present application has an advantageous structure in terms of tortuosity, and it can be confirmed that the cell diffusion resistance can be improved through the improvement of the conductive path, and thus the life durability of the lithium secondary battery is increased. there was.

Abstract

La présente invention concerne une composition d'électrode négative, une électrode négative pour une batterie secondaire au lithium la comprenant, une batterie secondaire au lithium comprenant l'électrode négative, et un procédé de préparation de la composition d'électrode négative.
PCT/KR2022/014845 2021-10-05 2022-09-30 Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative WO2023059015A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202280031910.9A CN117256057A (zh) 2021-10-05 2022-09-30 负极组合物、包含其的锂二次电池用负极、包含负极的锂二次电池、以及负极组合物的制备方法
JP2023566704A JP2024515382A (ja) 2021-10-05 2022-09-30 負極組成物、これを含むリチウム二次電池用負極、負極を含むリチウム二次電池、および負極組成物の製造方法
CA3220435A CA3220435A1 (fr) 2021-10-05 2022-09-30 Composition d'electrode negative, electrode negative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une electrode negative, et procede de preparation de composition d'electrode negative
EP22878836.0A EP4322248A1 (fr) 2021-10-05 2022-09-30 Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20210131869 2021-10-05
KR10-2021-0131869 2021-10-05
KR1020220007659A KR20230048997A (ko) 2021-10-05 2022-01-19 음극 조성물, 이를 포함하는 리튬 이차 전지용 음극, 음극을 포함하는 리튬 이차 전지 및 음극 조성물의 제조 방법
KR10-2022-0007659 2022-01-19

Publications (1)

Publication Number Publication Date
WO2023059015A1 true WO2023059015A1 (fr) 2023-04-13

Family

ID=85775462

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/014845 WO2023059015A1 (fr) 2021-10-05 2022-09-30 Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative

Country Status (6)

Country Link
US (1) US20230104135A1 (fr)
EP (1) EP4322248A1 (fr)
JP (1) JP2024515382A (fr)
KR (1) KR20230049029A (fr)
CA (1) CA3220435A1 (fr)
WO (1) WO2023059015A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117080420A (zh) * 2023-10-16 2023-11-17 瑞浦兰钧能源股份有限公司 一种负极片及电池

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009080971A (ja) 2007-09-25 2009-04-16 Tokyo Univ Of Science リチウムイオン電池用負極
JP2011065934A (ja) * 2009-09-18 2011-03-31 Osaka Titanium Technologies Co Ltd 珪素酸化物およびリチウムイオン二次電池用負極材
KR20130101097A (ko) * 2010-12-07 2013-09-12 오사카 티타늄 테크놀로지스 캄파니 리미티드 리튬 이온 이차 전지 음극재용 분말, 이것을 이용한 리튬 이온 이차 전지 음극 및 캐패시터 음극, 및 리튬 이온 이차 전지 및 캐패시터
KR20140012351A (ko) * 2012-07-19 2014-02-03 엠케이전자 주식회사 이차 전지용 음극 활물질 및 이를 포함하는 이차 전지
KR20150018088A (ko) * 2013-08-09 2015-02-23 오씨아이 주식회사 음극활물질용 실리콘 슬러리 및 탄소-실리콘 복합체
KR20210094685A (ko) * 2020-01-21 2021-07-30 대주전자재료 주식회사 규소-규소 복합산화물-탄소 복합체, 이의 제조방법 및 이를 포함하는 음극 활물질
KR20210131869A (ko) 2020-04-24 2021-11-03 이경환 텃밭과 수경의 복합재배 및 가습기능을 병행하는 고온소성볼 상토를 이용한 복합재배 키트
KR20220007659A (ko) 2019-05-24 2022-01-18 크노르-브렘제 시스테메 퓌어 누츠파조이게 게엠베하 상용 차량의 스티어링 너클, 상용 차량의 차축 조립체 및 차량 차축

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009080971A (ja) 2007-09-25 2009-04-16 Tokyo Univ Of Science リチウムイオン電池用負極
JP2011065934A (ja) * 2009-09-18 2011-03-31 Osaka Titanium Technologies Co Ltd 珪素酸化物およびリチウムイオン二次電池用負極材
KR20130101097A (ko) * 2010-12-07 2013-09-12 오사카 티타늄 테크놀로지스 캄파니 리미티드 리튬 이온 이차 전지 음극재용 분말, 이것을 이용한 리튬 이온 이차 전지 음극 및 캐패시터 음극, 및 리튬 이온 이차 전지 및 캐패시터
KR20140012351A (ko) * 2012-07-19 2014-02-03 엠케이전자 주식회사 이차 전지용 음극 활물질 및 이를 포함하는 이차 전지
KR20150018088A (ko) * 2013-08-09 2015-02-23 오씨아이 주식회사 음극활물질용 실리콘 슬러리 및 탄소-실리콘 복합체
KR20220007659A (ko) 2019-05-24 2022-01-18 크노르-브렘제 시스테메 퓌어 누츠파조이게 게엠베하 상용 차량의 스티어링 너클, 상용 차량의 차축 조립체 및 차량 차축
KR20210094685A (ko) * 2020-01-21 2021-07-30 대주전자재료 주식회사 규소-규소 복합산화물-탄소 복합체, 이의 제조방법 및 이를 포함하는 음극 활물질
KR20210131869A (ko) 2020-04-24 2021-11-03 이경환 텃밭과 수경의 복합재배 및 가습기능을 병행하는 고온소성볼 상토를 이용한 복합재배 키트

Also Published As

Publication number Publication date
JP2024515382A (ja) 2024-04-09
KR20230049029A (ko) 2023-04-12
US20230104135A1 (en) 2023-04-06
EP4322248A1 (fr) 2024-02-14
CA3220435A1 (fr) 2023-04-13

Similar Documents

Publication Publication Date Title
WO2021066560A1 (fr) Électrode positive et accumulateur la comprenant
WO2023282684A1 (fr) Anode pour batterie secondaire au lithium, procédé de fabrication d'anode pour batterie secondaire au lithium et batterie secondaire au lithium comprenant une anode
WO2023059015A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative
WO2021251663A1 (fr) Anode et batterie secondaire la comprenant
WO2023113464A1 (fr) Composition d'anode, anode de batterie secondaire au lithium la comprenant et batterie secondaire au lithium comprenant l'anode
WO2021125827A1 (fr) Électrode négative et batterie secondaire comprenant cette électrode négative
WO2022010225A1 (fr) Anode, et batterie rechargeable comprenant cette anode
WO2023055215A1 (fr) Composition d'anode, anode pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une anode, et procédé de préparation de la composition d'anode
WO2023059151A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium comprenant celle-ci, batterie secondaire au lithium comprenant une électrode négative et procédé de préparation de la composition d'électrode négative
WO2023068601A1 (fr) Anode pour batterie secondaire au lithium, batterie secondaire au lithium comprenant une anode, et procédé de fabrication d'anode pour batterie secondaire au lithium
WO2023059149A1 (fr) Solution de prédispersion d'anode, composition d'anode la comprenant, anode pour batterie secondaire au lithium comprenant une composition d'anode, batterie secondaire au lithium comprenant une anode et procédé de fabrication d'une composition d'anode
WO2023085691A1 (fr) Composition d'anode, anode pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une anode, et procédé de préparation de la composition d'anode
WO2024054019A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, et batterie secondaire au lithium comprenant une électrode négative
WO2023055216A1 (fr) Solution de dispersion préalable d'électrode négative, composition d'électrode négative la comprenant, électrode négative pour batterie secondaire au lithium comprenant une composition d'électrode négative, batterie secondaire au lithium comprenant une électrode négative, et procédé de production de composition d'électrode négative
WO2023121257A1 (fr) Composition d'anode, anode la comprenant pour batterie secondaire au lithium, batterie secondaire au lithium comprenant l'anode, et procédé de préparation de composition d'anode
WO2023068838A1 (fr) Composition d'anode, anode de batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une anode, et procédé de préparation de la composition d'anode
WO2023068880A1 (fr) Solution de pré-dispersion d'anode, composition d'anode la comprenant, anode pour batterie secondaire au lithium comprenant une composition d'anode, batterie secondaire au lithium comprenant une anode, et procédé de préparation de la composition d'anode
WO2023167449A1 (fr) Procédé de production de batterie secondaire au lithium et batterie secondaire au lithium
WO2023113462A1 (fr) Composition d'anode, anode pour batterie secondaire au lithium la comprenant et batterie secondaire au lithium comprenant l'anode
WO2023101426A1 (fr) Anode pour batterie secondaire au lithium, procédé de fabrication d'anode pour batterie secondaire au lithium et batterie secondaire au lithium comprenant une anode
WO2024014897A1 (fr) Matériau actif d'anode, procédé de fabrication de matériau actif d'anode, composition d'anode, anode pour batterie secondaire au lithium, comprenant celui-ci, et batterie secondaire au lithium comprenant une anode
WO2023249446A1 (fr) Électrode négative destinée à une batterie secondaire au lithium, procédé de fabrication d'électrode négative destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une électrode négative
WO2024085708A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium comprenant celle-ci, et batterie secondaire au lithium comprenant une électrode négative
WO2023120966A1 (fr) Composition d'anode, anode de batterie secondaire au lithium la comprenant, et batterie secondaire au lithium comprenant une anode
WO2024049235A1 (fr) Matériau actif négatif, son procédé de préparation, composition d'électrode négative, électrode négative comprenant celle-ci pour batterie secondaire au lithium, et batterie secondaire au lithium comprenant une électrode négative

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22878836

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023566704

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280031910.9

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2022878836

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 3220435

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2022878836

Country of ref document: EP

Effective date: 20231109